Composition for forming silica based insulating layer, silica based insulating layer and method for manufacturing silica based insulating layer

ABSTRACT

A composition for forming a silica-based insulation layer, a silica-based insulation layer, and a method of manufacturing the silica-based insulation layer, the composition including a solvent; and an organosilane-based condensation polymerization product, the organosilane-based condensation polymerization product being prepared from a compound mixture, the compound mixture including compounds represented by the following Chemical Formulae 1 and 2: 
       (R 1 ) 3 SiXSi(R 1 ) 3   [Chemical Formula 1]
 
       R 2   e (Si)OR 3   4-e .  [Chemical Formula 2]

CROSS-REFERENCE TO RELATED APPLICATION

Korean Patent Application No. 10-2013-0094277, filed on Aug. 8, 2013, in the Korean Intellectual Property Office, and entitled: “Composition for Forming Silica Based Insulating Layer, Silica Based Insulating Layer and Method for Manufacturing Silica Based Insulating Layer,” is incorporated by reference herein in its entirety.

BACKGROUND

1. Field

Embodiments relate to a composition for forming a silica-based insulation layer, a silica-based insulation layer, and a method of manufacturing the silica-based insulation layer.

2. Description of the Related Art

Due to accelerating development of semiconductor technologies, a highly-integrated and high-speed semiconductor memory cell having improved performance by increasing integration of a semiconductor chip having a smaller size has been considered.

SUMMARY

Embodiments are directed to a composition for forming a silica-based insulation layer, a silica-based insulation layer, and a method of manufacturing the silica-based insulation layer.

The embodiments may be realized by providing a composition for forming a silica-based insulation layer, the composition including a solvent; and an organosilane-based condensation polymerization product, the organosilane-based condensation polymerization product being prepared from a compound mixture, the compound mixture including compounds represented by the following Chemical Formulae 1 and 2:

(R¹)₃SiXSi(R¹)₃  [Chemical Formula 1]

wherein, in the above Chemical Formula 1, R¹ is independently hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C20 alkoxy group, a halogen-containing group, a silicon-containing group, or a combination thereof, and X is a porogen-containing linking group,

R² _(e)(Si)(OR³)_(4-e),  [Chemical Formula 2]

wherein, in the above Chemical Formula 2, e is an integer of 0 to 3, R² is independently hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a vinyl group, or a combination thereof, and R³ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a vinyl group, or a combination thereof.

The porogen may include polyethylene oxide (PEO), polypropylene oxide (PPO), or a copolymer of polyethylene oxide and polypropylene oxide.

The composition may further include a pore-forming agent.

The composition may further include a thermal acid generator.

The compound mixture may further include a compound represented by the following Chemical Formula 3:

(R⁴)₃Si(CH₂)_(m)Si(R⁴)₃  [Chemical Formula 3]

wherein, in the above Chemical Formula 3, m is an integer of 1 to 6, and R⁴ is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C20 alkoxy group, a halogen-containing group, a silicon-containing group, or a combination thereof.

The organosilane-based condensation polymerization product may include a structural unit represented by the following Chemical Formula 4:

wherein, in the above Chemical Formula 4, R¹ to R⁴, X, and M are the same as described with respect to Chemical Formulae 1 to 3, and x, y, and z represent a relative mole ratio of each repeating unit, and satisfy the following relations: 0.05≦x≦0.50, 0.45≦y≦0.90, 0.05≦z≦0.50, and x+y+z=1.

The organosilane-based condensation polymerization product may have a weight average molecular weight (Mw) of about 3,000 to about 20,000.

The organosilane-based condensation polymerization product may be included in an amount of about 0.1 to about 50 wt %, based on a total weight of the composition.

The embodiments may be realized by providing a silica-based insulation layer prepared from the composition for forming a silica-based insulation layer according to an embodiment.

The insulation layer may have a dielectric constant (k) of about 1.9 to about 3.5.

The insulation layer may have a modulus (E) of about 3 GPa to about 12 GPa.

The embodiments may be realized by providing a method of manufacturing a silica-based insulation layer, the method including coating the composition for forming a silica-based insulation layer according to an embodiment on a substrate; drying the substrate coated with the composition for forming a silica-based insulation layer; and curing the resultant at about 150° C. to about 500° C. under an inert gas atmosphere.

DETAILED DESCRIPTION

Example embodiments will now be described more fully hereinafter; however, they may be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey exemplary implementations to those skilled in the art.

As used herein, when a definition is not otherwise provided, the term ‘substituted’ refers to one substituted with a substituent selected from deuterium (D), a halogen atom (F, Cl, Br, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C4 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, or a combination thereof, instead of hydrogen of a compound.

As used herein, when a definition is not otherwise provided, the term ‘hetero’ refers to one including 1 to 3 heteroatoms selected from N, O, S, and P.

Hereinafter, a composition for forming a silica-based insulation layer according to an embodiment is described.

A composition for forming a silica-based insulation layer according to an embodiment may include a solvent and an organosilane-based condensation polymerization product. The organosilane-based condensation polymerization product may be prepared from a compound mixture, the compound mixture including compounds represented by the following Chemical Formulae 1 and 2.

(R¹)₃SiXSi(R¹)₃  [Chemical Formula 1]

In the above Chemical Formula 1,

R¹ may be hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C20 alkoxy group, a halogen-containing group, a silicon-containing group, or a combination thereof, and

X may be a porogen-containing linking group.

R² _(e)(Si)(OR³)_(4-e)  [Chemical Formula 2]

In the above Chemical Formula 2,

e may be an integer of 0 to 3,

R² may be hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a vinyl group, or a combination thereof, and

R³ may be hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a vinyl group, or a combination thereof.

The compound represented by Chemical Formula 1 may be a silane compound including a porogen-containing linking group (e.g., a porogen-bridged silane compound).

In the above Chemical Formula 1, the linking group represented by X may be linked to silicon atoms positioned at sides thereof and may include porogen.

The porogen may be a functional group that is decomposable at a temperature of about 150° C. to about 500° C. For example, the porogen may include a polyethylene oxide (PEO), a polypropylene oxide (PPO), or a copolymer of the polyethylene oxide and the polypropylene oxide.

In an implementation, more than two kinds of the porogen may be included. More than the two kinds of the porogen may have a mixing ratio adjusted to control a desired pore size.

As noted above, in Chemical Formula 1, R′ may be hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C20 alkoxy group, a halogen-containing group, a silicon-containing group, or a combination thereof.

The halogen-containing group may be a functional group including a halogen element (e.g., F, Cl, Br, or I).

The silicon-containing group may be a functional group including silicon (Si), e.g., —Si_(a)(OR)_(4-a). Herein, a may be an integer of 1 to 3, and R may be, e.g., hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a vinyl group, or a combination thereof.

The silicon-containing group may include, e.g., a silane, a silsesquioxane, or a combination thereof.

The organosilane-based condensation polymerization product may be prepared from the silane compound including a porogen-containing linking group and thus, may provide an insulation layer having a small pore size and small interconnection.

Examples of the compound of the above Chemical Formula 1 may include compounds represented by the following Chemical Formula 1-1 and Chemical Formula 1-2.

In the above Chemical Formulae 1-1 and 1-2, n may be an integer of 5 to 30.

The compound mixture for preparing the organosilane-based condensation polymerization product may further include a compound represented by the following Chemical Formula 3.

(R⁴)₃Si(CH₂)_(m)Si(R⁴)₃  [Chemical Formula 3]

In the above Chemical Formula 3,

m may be an integer of 1 to 6, and

R⁴ may be hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C20 alkoxy group, a halogen-containing group, a silicon-containing group, or a combination thereof.

In (CH₂)_(m) (indicating a linking group in the above Chemical Formula 3), m may be 1 to 6, e.g., 1 to 3.

The organosilane-based condensation polymerization product may include a structural unit represented by the following Chemical Formula 4.

In the above Chemical Formula 4,

R¹ to R⁴ may be the same as defined with respect to Chemical Formulae 1 to 3, above. For example, R¹ to R⁴ (while still keeping within the examples above) may each independently include one selected from hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a vinyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a hydroxy group, a halogen-containing group, a silicon-containing group, or a combination thereof.

X may be a porogen-containing linking group, and m may be an integer of 1 to 6, e.g., 1 to 3.

x, y, and z represent a relative mole ratio of each repeating unit, and may satisfy the following relations: 0.05≦x≦0.50, 0.45≦y≦0.90, 0.05≦z≦0.50, and x+y+z=1.

First, second, and third repeating units bracketed by the x, y and z may be arranged in order or may be randomly arranged. In an implementation, more than two out of the first, second, and third repeating units may be included, if desired.

The organosilane-based condensation polymerization product may include the structural unit represented by the above Chemical Formula 4 and thus may provide a low dielectric constant and may simultaneously have high hardness and modulus (e.g., Young's modulus E).

The organosilane-based condensation polymerization product may have a weight average molecular weight (Mw) of about 3,000 to about 20,000, e.g., about 4,000 to about 10,000.

The composition for forming a silica-based insulation layer may further include a pore-forming agent.

The pore-forming agent may include, e.g., polyalkyl glycol dialkoxy ethers or polyalkyl glycol methyl ethers.

The pore-forming agent may have, e.g., a molecular weight of about 300 to about 5,000, and a polydispersity of less than or equal to about 1.7.

The pore-forming agent may include, e.g., at least one selected from polyethylene glycol, polytetramethylene glycol, polyethylene glycol dimethyl ether, polypropylene glycol monobutyl ether, polyvinyl alcohol, polypropylene glycol, or polyhydroxybutyrate.

The composition for forming a silica-based insulation layer may further include a thermal acid generator (TAG).

The thermal acid generator may be an additive to help improve developability of the composition for forming a silica-based insulation layer, and may facilitate development of the organosilane-based condensation polymerization product in the composition at a relatively low temperature.

The thermal acid generator may include a suitable compound that generates acid (H⁺) by heat. For example, the thermal acid generator may include a compound that is activated at about 90° C. or higher and that generates sufficient acid, and that has low volatility.

The thermal acid generator may include, e.g., a compound represented by the following Chemical Formula 5.

R⁵ ₄N⁺A  [Chemical Formula 5]

In Chemical Formula 5,

R⁵ may be hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a halogen-containing group, a silicon-containing group, or a combination thereof.

A may be NO₃ ⁻ or dodecyl benzenesulfonate.

In an implementation, the thermal acid generator may be selected from, e.g., nitrobenzyl tosylate, nitrobenzyl benzenesulfonate, phenol sulfonate, and a combination thereof.

The thermal acid generator may be included in an amount of about 0.01 to about 25 wt %, based on the total weight of the composition for forming a silica-based insulation layer. Within the range, the condensation polymerization product may be developed at a relatively low temperature and may simultaneously exhibit improved coating properties.

In an implementation, the composition for forming a silica-based insulation layer may further include a surfactant.

The surfactant may include, e.g., a non-ionic surfactant such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, or the like, polyoxyethylene alkylallyl ethers such as polyoxyethylenenonyl phenol ether, or the like, polyoxyethylene•polyoxypropylene block copolymers, polyoxyethylene sorbitan fatty acid ester such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monoleate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, or the like; a fluorine-based surfactant of EFTOP EF301, EF303, EF352 (Tochem Products Co., Ltd.), MEGAFACE F171, F173 (Dainippon Ink & Chem., Inc.), FLUORAD FC430, FC431 (Sumitomo 3M), Asahi guardAG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), or the like; other silicone-based surfactant such as an organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.), or the like.

The surfactant may be included in an amount of about 0.001 wt % to about 10 wt %, based on the total weight of the composition for forming a silica-based insulation layer. Within the range, dispersion of a solution and simultaneously, uniform thickness of a layer and filling properties may be improved.

The composition for forming a silica-based insulation layer may be a solution where the organosilane-based condensation polymerization product and the other components are dissolved in a solvent.

The solvent may be a suitable solvent that is capable of dissolving the components. The solvent may include, e.g., alcohols such as methanol, ethanol and the like; ethers such as dichloroethyl ether, di-n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran and the like; glycol ethers such as ethylene glycol monomethylether, ethylene glycol monoethylether, and the like; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, diethyl cellosolve acetate, and the like; carbitols such as methylethyl carbitol, diethyl carbitol, diethylene glycol monomethylether, diethylene glycol monoethylether, diethylene glycol dimethylether, diethylene glycol methylethylether, diethylene glycol diethylether, and the like; propylene glycol alkylether acetates such as propylene glycol methylether acetate, propylene glycol propylether acetate, and the like; aromatic hydrocarbons such as toluene, xylene, and the like; ketones such as methylethylketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propylketone, methyl-n-butylketone, methyl-n-amylketone, 2-heptanone, and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, and the like; lactic acid esters such as methyl lactate, ethyl lactate, and the like; oxy alkyl acetate esters such as oxy methyl acetate, oxy ethyl acetate, oxy butyl acetate, and the like; alkoxy acetic acid alkyl esters such as methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethoxy ethyl acetate, and the like; 3-oxy alkyl propionate esters such as 3-oxy methyl propionate, 3-oxy ethyl propionate, and the like; 3-alkoxy alkyl propionate esters such as 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-ethoxy ethyl propionate, 3-ethoxy methyl propionate, and the like; 2-oxy alkyl propionate esters such as 2-oxy methyl propionate, 2-oxy ethyl propionate, 2-oxy propyl propionate, and the like; 2-alkoxy alkyl propionate esters such as 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-ethoxy ethyl propionate, 2-ethoxy methyl propionate, and the like; 2-oxy-2-methyl propionate esters such as 2-oxy-2-methyl methyl propionate, 2-oxy-2-methyl ethyl propionate and the like, 2-monooxy monocarboxylic acid alkyl esters of alkoxy-2-methyl alkyl propionate such as 2-methoxy-2-methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate and the like; esters such as 2-hydroxy ethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy ethyl acetate, 2-hydroxy-3-methyl methyl butanoate, and the like; ketonate esters such as ethyl pyruvate, and the like. In an implementation, a solvent having a high boiling point such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acethylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzylalcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, carbonate ethylene, carbonate propylene, phenyl cellosolve acetate, or the like may be added. In an implementation, at least one selected from diethylene glycolmonomethylether, diethylene glycoldiethylether, ethyl-3-ethoxy propionate, methyl-3-methoxy propionate, cyclopentanone, cyclohexanone, propylene glycolmonomethyl ether acetate, propylene glycoldimethyletheracetate, 1-methoxy-2-propanol, ethyl lactate, cyclopentanone and hydroxyacetic acidethyl may be selected.

In an implementation, the solvent may include at least one solvent having a high boiling point. In this case, the solvent may help prevent generation of a void inside a gap when the gap is filled and also may be slowly volatilized and thus, may help increase film flatness.

The solvent may be included in a balance amount, except the above components, based on the total weight of a composition for forming a silica-based insulation layer.

According to another embodiment, a silica-based insulation layer may be manufactured using the composition for forming a silica-based insulation layer.

The insulation layer may have a low dielectric constant and may simultaneously secure excellent mechanical characteristics. For example, the insulation layer may have a dielectric constant (k) of about 1.9 to about 3.5 and a modulus (E) of about 3 GPa to about 12 GPa.

The dielectric constant (k) may be measured by using a DC measurement system having a Summit11971b (Casecade Microtech Inc.), 4156C (Agilent Technologies), and 4200-SCS (Keithley Instruments Inc.), and the modulus (E) may be measured using a TI750 Ubi (Hysistron Inc.).

According to another embodiment, a method of manufacturing a silica-based insulation layer may include coating the above composition for forming a silica-based insulation layer on a substrate; drying the substrate coated with the composition for forming a silica-based insulation layer; and curing the resultant at about 150° C. to about 500° C. under an inert gas atmosphere.

The substrate may be, e.g., a device substrate such as a semiconductor, liquid crystal, or the like.

The following Examples and Comparative Examples are provided in order to highlight characteristics of one or more embodiments, but it will be understood that the Examples and Comparative Examples are not to be construed as limiting the scope of the embodiments, nor are the Comparative Examples to be construed as being outside the scope of the embodiments. Further, it will be understood that the embodiments are not limited to the particular details described in the Examples and Comparative Examples.

Synthesis of Organic Silane-based Condensation Polymerization Product Comparative Synthesis Example 1

5 g of triethoxy silane, 5 g of methyltrimethoxysilane (MTMS), and 100 g of methylisobutylketone (MIBK) were put in a 250 ml 3-necked flask having a bar magnet for agitation, a cooling tube, and a rubber cap, and 10 g of a 5 ppm nitric acid aqueous solution was added thereto. Subsequently, the mixture was reacted at room temperature for 10 days and further reacted for 4 days more after its temperature was increased to 40° C., obtaining an organosilane-based condensation polymerization product.

The weight average molecular weight (Mw) of the product was 3,500, and its polydispersity index (PDI) was 2.0.

Comparative Synthesis Example 2

2.5 g of triethoxy silane, 2.5 g of 1,2-bistriethoxysilylethane, 5 g of methyltrimethoxysilane (MTMS), 10 g of polypropylene glycol monobutyl ether were added to 100 g of propylene glycol methylether acetate (PGMEA) in a 250 ml 3-necked flask having a bar magnet for agitation, a cooling tube, and a rubber cap, and 10 g of a 5 ppm nitric acid aqueous solution was added thereto. Subsequently, the mixture was reacted at room temperature for 10 days and further reacted for 4 days more after its temperature was increased up to 40° C., obtaining an organosilane-based condensation polymerization product.

The weight average molecular weight (Mw) of the product was 3,900, and its polydispersity index (PDI) was 2.1.

Synthesis Example 1

2.5 g of a compound represented by the following Chemical Formula 1-1 (Mw=1,500), 2.5 g of 1,2-bistriethoxysilylethane, 5 g of methyltrimethoxysilane (MTMS), and 5.0 g of polypropylene glycol monobutylether were added to 100 g of propylene glycol methylether acetate (PGMEA) in a 250 ml 3-necked flask having a bar magnet for agitation, a cooling tube, and a rubber cap, and 10 g of a 100 ppm nitric acid aqueous solution was added thereto at 0° C. Subsequently, the mixture was reacted at 50° C. for 1 day, a byproduct (alcohol, water, nitric acid, and the like) was removed through distillation under a reduced pressure, and the solvent was also removed, obtaining an organosilane-based condensation polymerization product.

The weight average molecular weight (Mw) of the product was 5,000, and its polydispersity index (PDI) was 2.2.

Synthesis Example 2

2.5 g of a compound represented by the following Chemical Formula 1-2 (Mw=1,500), 2.5 g of 1,2-bistriethoxysilylethane, 5 g of methyltrimethoxysilane (MTMS), and 5.0 g of polypropylene glycol monobutyl ether were added to 100 g of propylene glycol methylether acetate (PGMEA) in a 250 mΩ 3-necked flask having a bar magnet for agitation, a cooling tube, and a rubber cap, and 10 g of a 100 ppm nitric acid aqueous solution was added thereto at 0° C. Subsequently, the mixture was reacted at 50° C. for 1 day, a byproduct (alcohol, water, nitric acid, and the like) was removed through distillation under a reduced pressure, and the solvent was also removed, obtaining an organosilane-based condensation polymerization product.

The weight average molecular weight (Mw) of the product was 4,900, and its polydispersity index (PDI) was 2.2.

Manufacture of Silica-based Insulation Layer Comparative Example 1

The organosilane-based condensation polymerization product according to Comparative Synthesis Example 1 was spin-coated on a silicon wafer, baked at 150° C. for 1 minute, and then, allowed to stand for 30 minutes under a N₂ atmosphere after its temperature was increased up to 430° C., forming a 4,500 Å-thick insulation layer.

Comparative Example 2

The organosilane-based condensation polymerization product according to Comparative Synthesis Example 2 was spin-coated on a silicon wafer, baked at 150° C. for 1 minute, and then, allowed to stand for 30 minutes under a N₂ atmosphere after its temperature was increased up to 430° C., forming a 4,600 Å-thick insulation layer.

Comparative Example 3

0.5 wt % of tetrabutyl ammonium nitrate was added to the organosilane-based condensation polymerization product according to Comparative Synthesis Example 2, and the mixture was spin-coated on a silicon wafer and baked at 150° C. for 1 minute. Subsequently, the coated wafer was allowed to stand for 30 minutes under a N₂ atmosphere after its temperature was increased up to 300° C., forming a 4,900 Å-thick insulation layer.

Example 1

The organosilane-based condensation polymerization product according to Synthesis Example 1 was spin-coated on a silicon wafer, baked at 150° C. for 1 minute, and then, allowed to stand for 30 minutes after its temperature was increased up to 430° C., forming a 4,600 Å-thick insulation layer.

Example 2

The organosilane-based condensation polymerization product according to Synthesis Example 2 was spin-coated on a silicon wafer, baked at 150° C. for 1 minute, and allowed to stand for 30 minutes under a N₂ atmosphere after its temperature was increased up to 430° C., forming a 4,600 Å-thick insulation layer.

Example 3

The organosilane-based condensation polymerization product according to Synthesis Example 2 was mixed with 0.5 wt % of tetrabutyl ammonium nitrate, and the mixture was spin-coated on a silicon wafer and baked at 150° C. for 1 minute. Subsequently, the baked wafer was allowed to stand for 30 minutes under a N₂ atmosphere after its temperature was increased up to 430° C., forming a 4,600 Å-thick insulation layer.

Evaluation

Refractive index (n), dielectric constant (k), and modulus (E) of the insulation layers according to Comparative Examples 1 to 3 and Examples 1 to 3 were measured.

A device and condition for the measurement were as follows.

Refractive index and thickness: measured at a wavelength of 632.8 nm by using ST-4000 (K-Mac Inc.)

Modulus: measured by using TI750 Ubi (Hysistron Inc.)

Dielectric constant: measured by using a DC measurement system having Summit11971b (Cascade Microtech Inc.), 4156C (Agilent Technologies), and 4200-SCS (Keithley Instruments Inc.).

The measurement results are provided in Table 1, below.

TABLE 1 Thickness Modulus Hardness Dielectric (nm) (GPa) (GPa) Constant (k) Comparative 450 6.0 1.9 2.2 Example 1 Comparative 460 7.8 2.0 2.2 Example 2 Comparative 490 7.8 2.0 2.2 Example 3 Example 1 460 8.5 2.1 2.1 Example 2 460 8.2 2.1 2.1 Example 3 470 9.1 2.2 2.0

Referring to Table 1, the insulation layers according to Examples 1 to 3 exhibited a low dielectric constant and simultaneously exhibited excellent modulus characteristics, compared with the insulation layers according to Comparative Examples 1 to 3.

By way of summation and review, requirements of high integration of a semiconductor may narrow a distance among wires and thus, may bring about a RC delay, a cross-talk, deterioration of a response speed, or the like, which may cause a problem in terms of interconnection of the semiconductor. An insulation layer material having a low dielectric constant and also high hardness or modulus during integration of the semiconductor may be used.

The embodiments may provide an insulation layer that has a low dielectric constant and that simultaneously provides excellent mechanical characteristics.

Example embodiments have been disclosed herein, and although specific terms are employed, they are used and are to be interpreted in a generic and descriptive sense only and not for purpose of limitation. In some instances, as would be apparent to one of ordinary skill in the art as of the filing of the present application, features, characteristics, and/or elements described in connection with a particular embodiment may be used singly or in combination with features, characteristics, and/or elements described in connection with other embodiments unless otherwise specifically indicated. Accordingly, it will be understood by those of skill in the art that various changes in form and details may be made without departing from the spirit and scope of the present invention as set forth in the following claims. 

What is claimed is:
 1. A composition for forming a silica-based insulation layer, the composition comprising: a solvent; and an organosilane-based condensation polymerization product, the organosilane-based condensation polymerization product being prepared from a compound mixture, the compound mixture including compounds represented by the following Chemical Formulae 1 and 2: (R¹)₃SiXSi(R¹)₃  [Chemical Formula 1] wherein, in the above Chemical Formula 1, R¹ is independently hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C20 alkoxy group, a halogen-containing group, a silicon-containing group, or a combination thereof, and X is a porogen-containing linking group, R² _(e)(Si)(OR³)_(4-e)  [Chemical Formula 2] wherein, in the above Chemical Formula 2, e is an integer of 0 to 3, R² is independently hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a vinyl group, or a combination thereof, and R³ is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C20 aryl group, a vinyl group, or a combination thereof.
 2. The composition for forming a silica-based insulation layer as claimed in claim 1, wherein the porogen includes polyethylene oxide (PEO), polypropylene oxide (PPO), or a copolymer of polyethylene oxide and polypropylene oxide.
 3. The composition for forming a silica-based insulation layer as claimed in claim 1, further comprising a pore-forming agent.
 4. The composition for forming a silica-based insulation layer as claimed in claim 1, further comprising a thermal acid generator.
 5. The composition for forming a silica-based insulation layer as claimed in claim 1, wherein the compound mixture further includes a compound represented by the following Chemical Formula 3: (R⁴)₃Si(CH₂)_(m)Si(R⁴)₃  [Chemical Formula 3] wherein, in the above Chemical Formula 3, m is an integer of 1 to 6, and R⁴ is hydrogen, a hydroxy group, a substituted or unsubstituted C1 to C20 alkoxy group, a halogen-containing group, a silicon-containing group, or a combination thereof.
 6. The composition for forming a silica-based insulation layer as claimed in claim 5, wherein the organosilane-based condensation polymerization product includes a structural unit represented by the following Chemical Formula 4:

wherein, in the above Chemical Formula 4, R¹ to R⁴, X, and M are the same as described with respect to Chemical Formulae 1 to 3, and x, y, and z represent a relative mole ratio of each repeating unit, and satisfy the following relations: 0.05≦x≦0.50, 0.45≦y≦0.90, 0.05≦z≦0.50, and x+y+z=1.
 7. The composition for forming a silica-based insulation layer as claimed in claim 1, wherein the organosilane-based condensation polymerization product has a weight average molecular weight (Mw) of about 3,000 to about 20,000.
 8. The composition for forming a silica-based insulation layer as claimed in claim 1, wherein the organosilane-based condensation polymerization product is included in an amount of about 0.1 to about 50 wt %, based on a total weight of the composition.
 9. A silica-based insulation layer prepared from the composition for forming a silica-based insulation layer as claimed in claim
 1. 10. The silica-based insulation layer as claimed in claim 9, wherein the insulation layer has a dielectric constant (k) of about 1.9 to about 3.5.
 11. The silica-based insulation layer as claimed in claim 9, wherein the insulation layer has a modulus (E) of about 3 GPa to about 12 GPa.
 12. A method of manufacturing a silica-based insulation layer, the method comprising: coating the composition for forming a silica-based insulation layer as claimed in claim 1 on a substrate; drying the substrate coated with the composition for forming a silica-based insulation layer; and curing the resultant at about 150° C. to about 500° C. under an inert gas atmosphere. 